US5585327A - 4-substituted pyridyl-3-carbinol compositions and a co-herbicide - Google Patents

4-substituted pyridyl-3-carbinol compositions and a co-herbicide Download PDF

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US5585327A
US5585327A US08/236,300 US23630094A US5585327A US 5585327 A US5585327 A US 5585327A US 23630094 A US23630094 A US 23630094A US 5585327 A US5585327 A US 5585327A
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alkyl
alkoxy
sub
halogen
hydrocarbyl
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US08/236,300
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Hsiao-Ling Chin
Yi-Qiu Wei
Nhan H. Nguyen
Michael P. Ensminger
Linda Willitts
Derek P. Dagarin
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ZENECA LIMITE
Syngenta Ltd
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Zeneca Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
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    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Definitions

  • this invention relates to novel 4-substituted pyridyl-3-carbinols which exhibit unexpectedly desirable herbicidal activity.
  • this invention relates to herbicidal compositions comprising a pyridyl carbinol and a suitable carrier, to herbicidal compositions comprising a pyridyl carbinol and a complementary herbicide, to a method of controlling undesirable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a pyridyl carbinol compound and to intermediates useful in making such 4-substituted pyridyl-3-carbinol compounds.
  • U.S. Pat. No. 4,116,665 to Krumkalns discloses a method of regulating the growth of aquatic weeds employing compounds of the formula ##STR5## wherein, inter alia, R 1 may be hydrogen, R 2 may be (substituted)-phenyl and X may be hydroxyl or alkoxy.
  • this invention is directed to a compound of the formula (I): ##STR6## wherein: R 1 and R 5 are each independently halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, --OH, thiocyano, nitro or --N(R 11 )(R 12 );
  • R 2 , R 3 and R 4 are each independently hydrogen C 1 -C 6 alkyl, nitro, halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or --S(O) m --R 10 ;
  • R 6 , R 7 , and R 8 are each independently hydrogen halogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkynyl, nitro, --N(R 11 )(R 12 ), C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, cyano, --C(X)--R 10 or --S(O) m --R 10 ;
  • R 9 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )-alkyl, --S(O) m --R 10 , cyano, hydroxy, thiocyano, nitro or --N(R 11 )(R 12 );
  • A is oxygen or sulfur
  • n 0 or 1
  • R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C 1 -C 6 alkoxy or is of the formula --C(X)--R 10 , --C(O)--C(O)--R 10 , --S(O) 2 --R 10 or --P(X)(R 15 )--(R 16 );
  • X is O or S
  • R 10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R 11 )(R 12 );
  • R 11 and R 12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, or N(R 13 )(R 14 ) wherein R 13 and R 14 are each independently hydrogen, C 1 -C 6 alkyl or phenyl;
  • R 11 and R 12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 6 alkyl;
  • R 15 and R 16 are each independently C 1 -C 6 alkyl, C 1 -C 6 alkylthio or C 1 -C 6 alkoxy;
  • n O, 1 or 2;
  • R 1 is chloro or fluoro
  • R 5 is hydrogen, chloro, fluoro or methoxy
  • R 2 , R 3 , R 6 , R 7 , R 8 and R 9 are hydrogen; R is not hydrogen;
  • this invention is directed to a herbicidal composition
  • a herbicidal composition comprising:
  • R 1 and R 5 are each independently halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )-alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, --OH, thiocyano, nitro or --N(R 11 )(R 12 );
  • R 2 , R 3 and R 4 are each independently hydrogen, C 1 -C 6 alkyl, nitro, halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or --S(O) m --R 10 ;
  • R 6 , R 7 , and R 8 are each independently hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkynyl, nitro, --N(R 11 )(R 12 ), C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, cyano, --C(X)--R 10 or --S(O) m --R 10 ;
  • R 9 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, hydroxy, thiocyano, nitro or --N(R 11 )(R 12 );
  • A is oxygen or sulfur
  • n 0 or 1
  • R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C 1 -C 6 alkoxy or is of the formula --C(X)--R 10 , --C(O)--C(O)--R 10 , --S(O) 2 --R 10 or --P(X)(R 15 )--(R 16 );
  • X is O or S
  • R 10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R 11 )(R 12 );
  • R 11 and R 12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C 1 -C 6 )-alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, or N(R 13 )(R 14 ) wherein R 13 and R 14 are each independently hydrogen, C 1 -C 6 alkyl or phenyl;
  • R 11 and R 12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 6 alkyl;
  • R 15 and R 16 are each independently C 1 -C 6 alkyl, C 1 -C 6 alkylthio or C 1 -C 6 alkoxy;
  • n O, 1 or 2;
  • This invention also is directed to herbicidal compositions comprising a compound of formula (I), as defined above, together with a complementary herbicide, and an agriculturally acceptable carrier therefor.
  • this invention is directed to a method for controlling undesirable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a compound of the formula (Ia): ##STR8## wherein R 1 and R 5 are each independently halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, --OH, thiocyano, nitro or --N(R 11 )(R 12 );
  • R 2 , R 3 and R 4 are each independently hydrogen C 1 -C 6 alkyl, nitro, halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or --S(O) m --R 10 ;
  • R 6 , R 7 , and R 8 are each independently hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkynyl, nitro, --N(R 11 )(R 12 ), C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, cyano, --C(X)--R 10 or --S(O) m --R 10 ;
  • R 9 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, hydroxy, thiocyano, nitro or --N(R 11 )(R 12 );
  • A is oxygen or sulfur
  • n 0 or 1
  • R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C 1 -C 6 alkoxy or is of the formula --C(X)--R 10 , --C(O)--C(O)--R 10 , --S(O) 2 --R 10 or --P(X)(R 15 )(R 16 );
  • X is O or S
  • R 10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R 11 )(R 12 );
  • R 11 and R 12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C 1 -C 6 )-alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, or N(R 13 )(R 14 ) wherein R 13 and R 14 are each independently hydrogen, C 1 -C 6 alkyl or phenyl;
  • R 11 and R 12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 6 alkyl;
  • R 15 and R 16 are each independently C 1 -C 6 alkyl, C 1 -C 6 alkylthio, or C 1 -C 6 alkoxy;
  • n O, 1 or 2;
  • this invention is directed to a compound of the formula (II): ##STR9## wherein R 1 and R 5 are each independently halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, --OH, thiocyano, nitro or --N(R 11 )(R 12 );
  • R 2 , R 3 and R 4 are each independently hydrogen C 1 -C 6 alkyl, nitro, halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or --S(O) m --R 10 ;
  • R 6 , R 7 , and R 8 are each independently hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkynyl, nitro, --N(R 11 )(R 12 ), C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, cyano, --C(X)--R 10 or --S(O) m --R 10 ;
  • R 9 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, hydroxy, thiocyano, nitro or --N(R 11 )(R 12 );
  • n 0 or 1
  • R 10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R 11 )(R 12 );
  • R 11 and R 12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 ) alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, or N(R 13 )(R 14 ) wherein R 13 and R 14 are each independently hydrogen, C 1 -C 6 alkyl or phenyl;
  • R 11 and R 12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, and of which may be optionally substituted with C 1 -C 6 alkyl;
  • R 15 and R 16 are each independently C 1 -C 6 alkyl, C 1 -C 6 alkylthio, or C 1 -C 6 alkoxy;
  • n 0, 1 or 2;
  • R 5 is hydrogen, chloro, fluoro or methoxy
  • R 2 , R 3 , R 6 , R 7 , R 8 and R 9 are hydrogen
  • R 1 is not chloro or fluoro
  • novel herbicidal compounds of this invention are the formula (I): ##STR10## wherein: R 1 and R 5 are each independently halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )-alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 , cyano, --OH, thiocyano, nitro or --N(R 11 )(R 12 );
  • R 2 , R 3 and R 4 are each independently hydrogen, C 1 -C 6 alkyl, nitro, halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or --S(O) m --R 10 ;
  • R 6 , R 7 , and R 8 are each independently hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkynyl, nitro, --N(R 11 )(R 12 ), C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, cyano, --C(X)--R 10 or --S(O) m --R 10 ;
  • R 9 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, (C 1 -C 6 )alkoxy-(C 1 -C 6 )alkyl, --S(O) m --R 10 cyano hydroxy, thiocyano, nitro or --N(R 11 )(R 12 );
  • A is oxygen or sulfur
  • n 0 or 1
  • R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C 1 -C 6 alkoxy or is of the formula --C(X)--R 10 , --C(O)--C(O)--R 10 , --S(O) 2 --R 10 or --P(X)(R 15 )(R 16 );
  • X is O or S
  • R 10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R 11 )(R 12 );
  • R 11 and R 12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, or N(R 13 )(R 14 ) wherein R 13 and R 14 are each independently hydrogen, C 1 -C 6 alkyl or phenyl;
  • R 11 and R 12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 6 alkyl;
  • R 15 and R 16 are each independently C 1 -C 6 alkyl, C 1 -C 6 alkythio; or C 1 -C 6 alkoxy;
  • n 0, 1 or 2;
  • R 1 is chloro or fluoro
  • R 5 is hydrogen, chloro, fluoro or methoxy
  • R 2 , R 3 , R 6 , R 7 , R 8 and R 9 are hydrogen; R is not hydrogen;
  • R 1 is halogen
  • R 2 , R 3 and R 4 are hydrogen
  • R 5 is halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, nitro or --S(O) m --(C 1 -C 3 )alkyl wherein m is 0, 1 or 2;
  • R 6 , R 7 , R 8 and R 9 are each independently hydrogen, C 1 -C 6 alkyl, halogen or C 1 -C 6 alkoxy;
  • R is phenyl-(C 1 -C 3 )alkyl or is of the formula ##STR11## wherein R 12 is C 1 -C 12 alkyl, C 1 -C 6 haloalkyl, phenyl or is of the formula ##STR12## wherein R 13 and R 14 are each independently C 1 -C 12 alkyl, hydrogen C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 haloalkyl, C 1 -C 6 alkoxy, (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl or R 13 and R 14 together with the nitrogen to which they are bound form a morpholine, piperidine or pyrrolidine ring.
  • R 1 is chloro or bromo
  • R 5 is trifluoromethyl, trifluoromethoxy, chloro, bromo, methoxy, methyl or ethyl;
  • R 2 , R 3 , R 4 , R 7 and R 8 are hydrogen
  • R 6 and R 9 are each independently hydrogen, chloro or methyl
  • R is benzyl or is of the formula ##STR13## wherein R 12 is C 1 -C 6 alkyl or is of the formula ##STR14## wherein R 13 and R 14 are independently hydrogen, phenyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkyl or together R 13 and R 14 form a morpholine ring.
  • Particularly preferred compounds include;
  • the compounds of such formulae can exist in enantiomeric forms.
  • the invention includes both individual enantiomers and mixtures of the two in all proportions.
  • hydrocarbyl whether representing a substituent on its own or whether it is part of the definition of a larger group (e.g., as in hydrocarbyloxy, hydrocarbyl-S(O) m --, etc.) is intended to include hydrocarbyl groups having from 1 to 12 carbon atoms.
  • hydrocarbyl therefore includes, for example, C 1 to C 12 alkyl including both straight and branched chain isomers (e.g., methyl, ethyl, propyl, and hexyl); cycloalkyl of 3 to 12 carbon atoms (e.g., cyclopropyl, cyclobutyl and cyclohexyl); C 2 to C 12 alkenyl including for example allyl and crotyl; C 2 to C 12 alkynyl (e.g., propynyl); phenyl; phenylalkyl; alkylphenyl, alkenylphenyl, alkynylphenyl, alkylbenzyl, alkenylbenzyl, alkynyl benzyl, naphthyl and the like.
  • C 1 to C 12 alkyl including both straight and branched chain isomers (e.g., methyl, ethyl, propyl, and
  • substituted hydrocarbyl is intended to include hydrocarbyl groups, as defined above, having one or more substituents selected from the group consisting of halogen (i.e., fluorine, chlorine, bromine, and iodine); C 1-4 alkoxy; C 1-4 alkyl-S(O) m --; cyano; carboxy, and salts, amides and esters thereof; alkanoyl of 2 to 4 carbon atoms; and phenyl optionally substituted by one or more C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkyl-S(O) m --, nitro, fluorine, chlorine, bromine, cyano, or CF 3 groups.
  • halogen i.e., fluorine, chlorine, bromine, and iodine
  • C 1-4 alkoxy i.e., fluorine, chlorine, bromine, and iodine
  • C 1-4 alkoxy i.e., chlorine, bromine, and
  • the hydrocarbyl radical is a substituted aryl radical (e.g., phenyl, benzyl or naphthyl)
  • the substituents may include one or more of the substituents listed in the last foregoing paragraph, and may also include nitro.
  • salts, amides, and esters thereof used above in relation to carboxy substitution includes, for example, salts formed from alkali metal (e.g., sodium, potassium, and lithium), alkaline earth metals (e.g., calcium and magnesium), the ammonium ion, and substituted ammonium ions wherein one, two, three, or four of the hydrogen atoms have been replaced by optionally substituted C 1-6 hydrocarbyl moieties as defined above.
  • alkali metal e.g., sodium, potassium, and lithium
  • alkaline earth metals e.g., calcium and magnesium
  • ammonium ion e.g., sodium, potassium, and lithium
  • substituted ammonium ions wherein one, two, three, or four of the hydrogen atoms have been replaced by optionally substituted C 1-6 hydrocarbyl moieties as defined above.
  • halogen includes fluoro, chloro, bromo and iodo groups. In polyhalogenated groups the halogens may be the same or different.
  • the compounds of the present invention have been found to be active herbicides, possessing utility as pre-emergence and post-emergence herbicides and useful against a wide range of plant species including broadleaf and grassy species.
  • This invention therefore also relates to a method for controlling undesirable vegetation comprising applying to a locus where control of such vegetation is desired, either prior or subsequent to the emergence of such vegetation, a herbicidally effective amount of a compound as described herein, together with an inert diluent or carrier suitable for use with herbicides.
  • herbicide and “herbicidal” are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development such as, for example, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing.
  • herbicidally effective amount is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing.
  • plants is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.
  • agriculturally acceptable salt is easily determined by one of ordinary skill in the art and includes hydrohalogen, acetic, sulfonic, phosphonic, inorganic and organic acid salts.
  • the compounds of this invention are prepared by (A) reacting a substituted pyridine of the formula (III): ##STR15## with a substituted benzaldehyde of the formula (IV): ##STR16## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined for formula (I) above; in the presence of a suitable base to form a 3-pyridyl carbinol of formula II above (without the proviso thereto being applicable); and, where appropriate, (B) reacting such pyridyl carbinol with an appropriate derivatizing agent (e.g., an alkyl or aryl acid halide, carbamoyl halide, alkyl halide, sulfonyl halide or phosphoryl halide) or an appropriate isocyanate, or sequentially first with phosgene or a phosgene equivalent and then with an appropriate an appropriate
  • an appropriate base such as lithium diisopropylamide or n-butyl lithium
  • a solvent such as ethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether or the like
  • a solvent such as ethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether or the like
  • This reaction mixture is typically agitated and slowly warmed up to ambient temperature (about 25° C.) over a period of 1-24 hours.
  • the reaction is then generally quenched by the addition of a saturated aqueous ammonium chloride solution or aqueous hydrochloric acid.
  • the pyridyl carbinol so produced may be recovered by conventional techniques (such as extraction, filtration and the like) and purified by known methods, e.g., flash chromatography.
  • the pyridyl carbinol (II), in a suitable solvent may typically be added to between about 1 and about 4 equivalents of an appropriate base (such as sodium hydride or triethylamine) at about 0° C.
  • an appropriate base such as sodium hydride or triethylamine
  • derivatizing agent such as a carbamoyl halide, an alkyl halide, sulfonyl halide or a phosphosphoryl halide, an alkyl or aryl acid halide
  • the reaction may be quenched by the addition of ice water, and the products recovered by conventional techniques, such as extraction, filtration and the like.
  • the product so recovered may then be purified by conventional techniques such as flash chromatography or the like.
  • the pyridyl carbinol in suitable solvent such as tetrahydrofuran, methylene chloride or the like
  • suitable solvent such as tetrahydrofuran, methylene chloride or the like
  • suitable solvent such as tetrahydrofuran, methylene chloride or the like
  • an appropriate isocyanate between about 2 and about 3 equivalents of an appropriate isocyanate.
  • one or more appropriate catalyst e.g., triethyl amine or dibutyl tin dilaurate
  • the product may be recovered by conventional techniques (such as extraction, filtration or the like) and may be purified by conventional techniques such as flash chromatography or the like.
  • the substituted pyridine starting materials of Formula (III) are either commercially available or may be prepared by one of ordinary skill in the art employing methods such as those described in "Heterocyclic Compounds, Pyridine and its Derivatives", R. A. Abramovitch, Vol 14, Wiley, 1973.
  • the aldehyde starting materials of Formula (IV) are commercially available or may be prepared employing techniques such as those described in "Survey of Organic Synthesis", C. A. Buehler et al., Vols. 1 and 2, Wiley-Interscience, 1970.
  • compositions of this invention comprise a compound of formula (Ia) above and a suitable carrier, which carriers are well known to one of ordinary skill in the art.
  • the compounds of the present invention are useful as herbicides and can be applied in a variety of ways known to those skilled in the art, at various concentrations.
  • the compounds are useful in controlling the growth of undesirable vegetation by pre-emergence or post-emergence application to the locus where control is desired.
  • the compounds are applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating dispersion. The choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly.
  • the compounds of the invention may thus be formulated as granules, as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as microcapsules. These formulations may contain as little as about 0.5% to as much as amount 95% or more by weight of active ingredient. The optimum amount for any given compound will depend upon the nature of the seeds or plants to be controlled. The rate of application will generally vary from about 0.01 to about 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles, and are usually applied without dilution to the area in which suppression of vegetation is desired.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain about 5% to about 25% active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplet are typically about 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurized sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
  • formulations include wetting, dispersing or emulsifying agents.
  • examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.
  • Each of the above formulations can be prepared as a package containing the herbicide together with other ingredients of the formulation (diluents, emulsifiers, surfactants etc.).
  • the formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
  • the compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provided a higher level of effectiveness in controlling weeds and often provide results unattainable with separate formulations of the individual herbicides.
  • Examples of useful complementary herbicides include:
  • B. hormone herbicides particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
  • 1,3-dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
  • D Dinitrophenols and their derivatives (e.g. acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
  • acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
  • arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron;
  • phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
  • uracil herbicides such as lenacil, bromacil and terbacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
  • K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepiperate;
  • N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
  • O. anilide herbicides such as pretilachlor, butachlor, the corresponding alachlor, the corresponding compound propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor;
  • P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
  • haloalkanoic herbicides such as dalapon, TCA and salts thereof;
  • diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
  • S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
  • T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
  • arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
  • X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos;
  • Y. organoarsenical herbicides such as MSMA
  • herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, (in the ratio 3:1) flurochloridone, quinchlorac and mefanacet;
  • useful contact herbicides include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.
  • co-herbicides for use in an herbicidal composition containing a compound of formula (I): anilide herbicides, triketone and cyclohexanedione herbicides, imidazolidinone herbicides, sulfonylurea herbicides and phenoxyphenoxypropionate herbicides.
  • anilide herbicides triketone and cyclohexanedione herbicides
  • imidazolidinone herbicides imidazolidinone herbicides
  • sulfonylurea herbicides sulfonylurea herbicides
  • phenoxyphenoxypropionate herbicides phenoxyphenoxypropionate herbicides.
  • specific examples of preferred co-herbicides for use in combination with the pyridyl carbinols of this invention are metolachlor, imazaquin, bensulfuron and the methyl ester thereof, chlorsulfuron and dichlofop.
  • Dust and liquid compositions can be applied by the use of power-dusters, boom and hand sprayers and spray dusters.
  • the formulations can also be applied from airplanes as a dust or a spray or by rope wick applications.
  • dust and liquid formulations can be distributed in the soil to a depth of at least one-half inch below the soil surface or applied to the soil surface only, by spraying or sprinkling.
  • the formulations can also be applied by addition to irrigation water. This permits penetration of the formulations into the soil together with the irrigation water. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.
  • These dusts are formed by mixing the components then grinding the mixture to the desired particle size.
  • Granules are formed by mixing the active compound with epichlorohydrin and dissolving the mixture in 6 parts of acetone. The polyethylene glycol and cetyl polyglycol ether are then added. The resultant solution is sprayed on the kaolin and the acetone evaporated in vacuo.
  • wettable powders are prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
  • Emulsifiable concentrate is a liquid crystal
  • compositions which constitute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled.
  • the rate of application of active ingredients varies from about 0.01 to about pounds per acre, preferably about 0.10 to about 10 pounds per acre with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.
  • LDA lithium diisopropyl amide
  • the soil surface was sprayed inside an enclosed linear spray table.
  • the flats were sprayed with the spray solution calibrated to deliver 748 L/ha.
  • the application rate was 4.0 or 1.0 kg/ha.
  • the flats were placed into a greenhouse at 21°-29° C. and water daily by sprinkling.
  • the degree of weed control was visually assessed and recorded 17-21 days after treatment, as percentage control compared to the growth of the same species of the same age in an untreated check flat.
  • the soil was prepared and seeded with the same species and methodology described for the pre-emergence test.
  • the flats were placed in the greenhouse at 21°-29° C. and watered by sprinkling.
  • the seeds of the weed species were planted 10-12 days before treatment.
  • grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage. Watering of the treated flats was confined to the soil surface and not to the foliage of the germinated plants.
  • the degree of weed control was visually assessed and recorded 17-21 days after treatment, as percentage control compared to the growth of the same species in an untreated check flat of the same age.
  • the percent control is the total injury to the plants due to all factors, including inhibited germination, killing of the plant tissue after emergence, stunting, malformation, chlorosis and other types of injury.
  • the control ratings vary from 0 to 100 percent, where 0 represents no effect with growth equal to the untreated control, and 100 represents complete kill; a dash indicates that a test was not performed at that level of application.

Abstract

4-substituted pyridyl-3-carbinols of the formula ##STR1## wherein R is hydrogen, or an acyl, alkyl or carbamyl group exhibit desirable preemergent and postemergent herbicidal activity. Also disclosed are herbicidal compositions comprising such compounds and methods of controlling undesirable vegetation employing such compounds. The compounds wherein AR is hydroxyl serve as useful intermediates for the production of the alpha-benzyl substituted compounds as well as exhibiting herbicidal activity.

Description

This application is a continuation-in-part of U.S. application Ser. No. 08/051,490, filed Apr. 22, 1993 now U.S. Pat. No. 5,308,826.
FIELD OF THE INVENTION
In one aspect, this invention relates to novel 4-substituted pyridyl-3-carbinols which exhibit unexpectedly desirable herbicidal activity. In other aspects, this invention relates to herbicidal compositions comprising a pyridyl carbinol and a suitable carrier, to herbicidal compositions comprising a pyridyl carbinol and a complementary herbicide, to a method of controlling undesirable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a pyridyl carbinol compound and to intermediates useful in making such 4-substituted pyridyl-3-carbinol compounds.
BACKGROUND OF THE INVENTION
The need for effective herbicides needs no special emphasis. The control of weeds and undesirable vegetation is of great economic importance since weed competition inhibits the production of foliage, fruit or seed of agricultural crops. The presence of weeds can reduce harvesting efficiency and the quality of the harvested crop. Weeds on noncropped areas may cause a fire hazard, undesirable drifting of sand or snow, and/or irritation to persons with allergies. Thus, suppression of undesirable weed growth is very advantageous.
Accordingly, it is an object of this invention to provide effective novel herbicidal compounds, as well as to provide a novel herbicidal composition and a novel method of controlling weeds. Further, it is an object of this invention to provide intermediates which, as well as exhibiting herbicidal activity, are also useful in the production of other herbicidally active compounds.
While certain 4-substituted pyridyl-3-carbinols are disclosed in the art, these disclosures contain no description of the utility of such compounds. Thus, Radinov et al., "Synthesis of 4-Amino-3-pyridinyl and 4-Amino-5-pyrimidinyl Aryl Ketones and Related Compounds via an ortho-Lithiation Reaction", Synthesis, pp. 886-891, November 1986, disclose inter alia at page 887, compounds of the formula ##STR2## wherein X2 is chlorine or fluorine.
Somewhat similarly, Marsais et al., "Directed Lithiation of 4-Halopyridines: Chemoselectivity, Regioselectivily and Application to Synthesis", J. Heterocyclic Chem., Vol 25, pp. 81-87 (1987), disclose the production of compounds of the formula ##STR3## wherein El is phenyl or 2-methoxyphenyl.
Certain (non-substituted)-pyridyl-3-carbinols of the formula ##STR4## are disclosed in U.S. Pat. No. 4,407,806 to Cherpeck (wherein R and R1 are as defined therein).
Similarly, U.S. Pat. No. 4,116,665 to Krumkalns discloses a method of regulating the growth of aquatic weeds employing compounds of the formula ##STR5## wherein, inter alia, R1 may be hydrogen, R2 may be (substituted)-phenyl and X may be hydroxyl or alkoxy.
SUMMARY OF THE INVENTION
In one aspect, this invention is directed to a compound of the formula (I): ##STR6## wherein: R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen halogen, C1 -C6 alkyl, C1 -C6 alkenyl, C1 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)-alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)--(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)alkoxycarbonyl(C1 -C6)alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio or C1 -C6 alkoxy; and
m is O, 1 or 2;
with the proviso that when R1 is chloro or fluoro; R5 is hydrogen, chloro, fluoro or methoxy; and R2, R3, R6, R7, R8 and R9 are hydrogen; R is not hydrogen;
and agriculturally acceptable salts thereof.
In another aspect, this invention is directed to a herbicidal composition comprising:
(A) A compound of the formula (Ia): ##STR7## wherein: R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)-alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen, C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C1 -C6 alkenyl, C1 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)--(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)-alkoxycarbonyl(C1 -C6)alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio or C1 -C6 alkoxy; and
m is O, 1 or 2;
or an agriculturally acceptable salt thereof; and
(B) a carrier therefor.
This invention also is directed to herbicidal compositions comprising a compound of formula (I), as defined above, together with a complementary herbicide, and an agriculturally acceptable carrier therefor.
In yet another aspect, this invention is directed to a method for controlling undesirable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a compound of the formula (Ia): ##STR8## wherein R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C1 -C6 alkenyl, C1 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)-alkoxycarbonyl(C1 -C6)alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio, or C1 -C6 alkoxy; and
m is O, 1 or 2;
and agriculturally acceptable salts thereof.
In yet a further aspect, because the compounds of this invention wherein AR is OH are useful intermediates for producing the other compounds of this invention, as well as possessing herbicidal activity, this invention is directed to a compound of the formula (II): ##STR9## wherein R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C1 -C6 alkenyl, C1 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
n is 0 or 1;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)alkoxycarbonyl(C1 -C6) alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, and of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio, or C1 -C6 alkoxy; and
m is 0, 1 or 2;
with the proviso that when R5 is hydrogen, chloro, fluoro or methoxy; and R2, R3, R6, R7, R8 and R9 are hydrogen; R1 is not chloro or fluoro;
and agriculturally acceptable salts thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The novel herbicidal compounds of this invention are the formula (I): ##STR10## wherein: R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)-alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen, C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C1 -C6 alkenyl, C1 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10 cyano hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)alkoxycarbonyl(C1 -C6)alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkythio; or C1 -C6 alkoxy; and
m is 0, 1 or 2;
with the proviso that when R1 is chloro or fluoro; R5 is hydrogen, chloro, fluoro or methoxy; and R2, R3, R6, R7, R8 and R9 are hydrogen; R is not hydrogen;
and agriculturally acceptable salts thereof.
Preferably,
R1 is halogen;
R2, R3 and R4 are hydrogen;
R5 is halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, nitro or --S(O)m --(C1 -C3)alkyl wherein m is 0, 1 or 2;
R6, R7, R8 and R9 are each independently hydrogen, C1 -C6 alkyl, halogen or C1 -C6 alkoxy; and
R is phenyl-(C1 -C3)alkyl or is of the formula ##STR11## wherein R12 is C1 -C12 alkyl, C1 -C6 haloalkyl, phenyl or is of the formula ##STR12## wherein R13 and R14 are each independently C1 -C12 alkyl, hydrogen C2 -C12 alkenyl, C2 -C12 alkynyl, C1 -C12 haloalkyl, C1 -C6 alkoxy, (C1 -C6)alkoxy(C1 -C6)alkyl or R13 and R14 together with the nitrogen to which they are bound form a morpholine, piperidine or pyrrolidine ring.
More preferably,
R1 is chloro or bromo;
R5 is trifluoromethyl, trifluoromethoxy, chloro, bromo, methoxy, methyl or ethyl;
R2, R3, R4, R7 and R8 are hydrogen;
R6 and R9 are each independently hydrogen, chloro or methyl; and
R is benzyl or is of the formula ##STR13## wherein R12 is C1 -C6 alkyl or is of the formula ##STR14## wherein R13 and R14 are independently hydrogen, phenyl, C1 -C6 haloalkyl or C1 -C6 alkyl or together R13 and R14 form a morpholine ring.
Particularly preferred compounds include;
4-chloro-3-(1-N,N-dimethylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N-methylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N,N-diethylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-[1-(4-morpholine)-carbonyloxy-2'trifluoromethylbenzyl]-pyridine;
4-chloro-3-(1-N-methyl-N-phenyl-carbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-trimethylacetoxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-[1-(2-N-chloroethylcarbamyloxy)-2'trifluoromethylbenzyl]-pyridine;
4-chloro-3-(1-N-ethylcarbamyloxy-2'trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N-isopropylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N-propylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-bromo-3-(1-N,N-dimethylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N,N-dimethyl-carbamyloxy-2'-chlorobenzyl)pyridine;
4-chloro-3-(1-N,N-dimethylcarbamyloxy-2'-methylbenzyl)-pyridine;
4-chloro-3-(1-N-methylcarbamyloxy-2'-bromobenzyl)pyridine;
4-chloro-3-(1-N,N-diallylcarbamyl-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N-methyl-N-ethyl-carbamyloxy-2'-trifluoromethylbenzyl)-pyridine;
4-chloro-3-(1-N-allylcarbamyloxy-2'-trifluoromethylbenzyl)-pyridine; and
4-chloro-3-(1-t-butylcarbonyloxy-2'-ethylbenzyl)pyridine.
The formulae given above are intended to include tautomeric forms of the structures drawn therein, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in relation to other parts, or from geometrical isomerism, or from intra-molecular or inter-molecular hydrogen bonding, or otherwise.
The compounds of such formulae can exist in enantiomeric forms. The invention includes both individual enantiomers and mixtures of the two in all proportions.
As is employed herein, the term "hydrocarbyl", whether representing a substituent on its own or whether it is part of the definition of a larger group (e.g., as in hydrocarbyloxy, hydrocarbyl-S(O)m --, etc.) is intended to include hydrocarbyl groups having from 1 to 12 carbon atoms. The term hydrocarbyl therefore includes, for example, C1 to C12 alkyl including both straight and branched chain isomers (e.g., methyl, ethyl, propyl, and hexyl); cycloalkyl of 3 to 12 carbon atoms (e.g., cyclopropyl, cyclobutyl and cyclohexyl); C2 to C12 alkenyl including for example allyl and crotyl; C2 to C12 alkynyl (e.g., propynyl); phenyl; phenylalkyl; alkylphenyl, alkenylphenyl, alkynylphenyl, alkylbenzyl, alkenylbenzyl, alkynyl benzyl, naphthyl and the like.
The term "substituted hydrocarbyl" is intended to include hydrocarbyl groups, as defined above, having one or more substituents selected from the group consisting of halogen (i.e., fluorine, chlorine, bromine, and iodine); C1-4 alkoxy; C1-4 alkyl-S(O)m --; cyano; carboxy, and salts, amides and esters thereof; alkanoyl of 2 to 4 carbon atoms; and phenyl optionally substituted by one or more C1-4 alkyl, C1-4 alkoxy, C1-4 alkyl-S(O)m --, nitro, fluorine, chlorine, bromine, cyano, or CF3 groups. In the above definitions, m is 0, 1 or 2.
Further, when the hydrocarbyl radical is a substituted aryl radical (e.g., phenyl, benzyl or naphthyl), the substituents may include one or more of the substituents listed in the last foregoing paragraph, and may also include nitro.
The expression "salts, amides, and esters thereof" used above in relation to carboxy substitution includes, for example, salts formed from alkali metal (e.g., sodium, potassium, and lithium), alkaline earth metals (e.g., calcium and magnesium), the ammonium ion, and substituted ammonium ions wherein one, two, three, or four of the hydrogen atoms have been replaced by optionally substituted C1-6 hydrocarbyl moieties as defined above.
Further, the above definitions the term "halogen" includes fluoro, chloro, bromo and iodo groups. In polyhalogenated groups the halogens may be the same or different.
The compounds of the present invention have been found to be active herbicides, possessing utility as pre-emergence and post-emergence herbicides and useful against a wide range of plant species including broadleaf and grassy species.
This invention therefore also relates to a method for controlling undesirable vegetation comprising applying to a locus where control of such vegetation is desired, either prior or subsequent to the emergence of such vegetation, a herbicidally effective amount of a compound as described herein, together with an inert diluent or carrier suitable for use with herbicides.
The terms "herbicide" and "herbicidal" are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development such as, for example, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing. The term "herbicidally effective amount" is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing. The term "plants" is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.
The term "agriculturally acceptable salt" is easily determined by one of ordinary skill in the art and includes hydrohalogen, acetic, sulfonic, phosphonic, inorganic and organic acid salts.
In general, the compounds of this invention are prepared by (A) reacting a substituted pyridine of the formula (III): ##STR15## with a substituted benzaldehyde of the formula (IV): ##STR16## wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined for formula (I) above; in the presence of a suitable base to form a 3-pyridyl carbinol of formula II above (without the proviso thereto being applicable); and, where appropriate, (B) reacting such pyridyl carbinol with an appropriate derivatizing agent (e.g., an alkyl or aryl acid halide, carbamoyl halide, alkyl halide, sulfonyl halide or phosphoryl halide) or an appropriate isocyanate, or sequentially first with phosgene or a phosgene equivalent and then with an appropriate amine, to produce the desired compound.
Typically, about 1-2 equivalents of an appropriate base (such as lithium diisopropylamide or n-butyl lithium) is added to a substituted pyridine of formula (III) in a solvent (such as ethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether or the like) at a temperature of between about -100° and about -40° C. After suitable blending, about 1-2 equivalents of the substituted benzaldehyde (IV) is generally added.
This reaction mixture is typically agitated and slowly warmed up to ambient temperature (about 25° C.) over a period of 1-24 hours. The reaction is then generally quenched by the addition of a saturated aqueous ammonium chloride solution or aqueous hydrochloric acid. The pyridyl carbinol so produced may be recovered by conventional techniques (such as extraction, filtration and the like) and purified by known methods, e.g., flash chromatography.
In the second step, the pyridyl carbinol (II), in a suitable solvent (such as tetrahydrofuran, methylene chloride, or the like) may typically be added to between about 1 and about 4 equivalents of an appropriate base (such as sodium hydride or triethylamine) at about 0° C. Between about 1 and about 3 equivalents of derivatizing agent (such as a carbamoyl halide, an alkyl halide, sulfonyl halide or a phosphosphoryl halide, an alkyl or aryl acid halide) is then added and the mixture agitated until complete. The reaction may be quenched by the addition of ice water, and the products recovered by conventional techniques, such as extraction, filtration and the like. The product so recovered may then be purified by conventional techniques such as flash chromatography or the like.
Alternatively, in the second step, the pyridyl carbinol in suitable solvent (such as tetrahydrofuran, methylene chloride or the like) may be added to between about 2 and about 3 equivalents of an appropriate isocyanate. Between about 1 and about 10 mole percent of one or more appropriate catalyst, e.g., triethyl amine or dibutyl tin dilaurate, may be added and the reaction mixture agitated at between about 0° and 100° C. for an appropriate period (e.g., 2 to 24 hours). The product may be recovered by conventional techniques (such as extraction, filtration or the like) and may be purified by conventional techniques such as flash chromatography or the like.
The substituted pyridine starting materials of Formula (III) are either commercially available or may be prepared by one of ordinary skill in the art employing methods such as those described in "Heterocyclic Compounds, Pyridine and its Derivatives", R. A. Abramovitch, Vol 14, Wiley, 1973. The aldehyde starting materials of Formula (IV) are commercially available or may be prepared employing techniques such as those described in "Survey of Organic Synthesis", C. A. Buehler et al., Vols. 1 and 2, Wiley-Interscience, 1970.
The compositions of this invention comprise a compound of formula (Ia) above and a suitable carrier, which carriers are well known to one of ordinary skill in the art.
The compounds of the present invention are useful as herbicides and can be applied in a variety of ways known to those skilled in the art, at various concentrations. The compounds are useful in controlling the growth of undesirable vegetation by pre-emergence or post-emergence application to the locus where control is desired. In practice, the compounds are applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating dispersion. The choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly. The compounds of the invention may thus be formulated as granules, as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as microcapsules. These formulations may contain as little as about 0.5% to as much as amount 95% or more by weight of active ingredient. The optimum amount for any given compound will depend upon the nature of the seeds or plants to be controlled. The rate of application will generally vary from about 0.01 to about 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles, and are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain about 5% to about 25% active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or granules of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplet are typically about 1 to 50 microns in diameter. The enclosed liquid typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
Many of these formulations include wetting, dispersing or emulsifying agents. Examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.
Each of the above formulations can be prepared as a package containing the herbicide together with other ingredients of the formulation (diluents, emulsifiers, surfactants etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provided a higher level of effectiveness in controlling weeds and often provide results unattainable with separate formulations of the individual herbicides.
Examples of other herbicides, defoliants, desiccants and plant growth inhibitors with which the compounds of this invention can be combined are:
Examples of useful complementary herbicides include:
A. Benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as bentazone;
B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
C. 1,3-dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
D. Dinitrophenols and their derivatives (e.g. acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron;
G. phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloridazon, and norflurazon;
I. uracil herbicides such as lenacil, bromacil and terbacil;
J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepiperate;
M. 1,2,4-triazin-5-one herbicides such as metamitron and metribuzin;
N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
O. anilide herbicides such as pretilachlor, butachlor, the corresponding alachlor, the corresponding compound propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor;
P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;
R. diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim, and clethodim;
U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos;
Y. organoarsenical herbicides such as MSMA;
Z. herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
AA. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, (in the ratio 3:1) flurochloridone, quinchlorac and mefanacet;
BB. examples of useful contact herbicides include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.
Of the above complementary herbicides, the following are preferred co-herbicides for use in an herbicidal composition containing a compound of formula (I): anilide herbicides, triketone and cyclohexanedione herbicides, imidazolidinone herbicides, sulfonylurea herbicides and phenoxyphenoxypropionate herbicides. From these classes of preferred co-herbicides, specific examples of preferred co-herbicides for use in combination with the pyridyl carbinols of this invention are metolachlor, imazaquin, bensulfuron and the methyl ester thereof, chlorsulfuron and dichlofop.
These formulations can be applied to the areas where control is desired by conventional methods. Dust and liquid compositions, for example, can be applied by the use of power-dusters, boom and hand sprayers and spray dusters. The formulations can also be applied from airplanes as a dust or a spray or by rope wick applications. To modify or control growth of germinating seeds or emerging seedlings, dust and liquid formulations can be distributed in the soil to a depth of at least one-half inch below the soil surface or applied to the soil surface only, by spraying or sprinkling. The formulations can also be applied by addition to irrigation water. This permits penetration of the formulations into the soil together with the irrigation water. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.
The following are examples of typical formulations.
______________________________________                                    
5% dust:    5     parts active compound                                   
            95    parts talc                                              
2% dust:    2     parts active compound                                   
            1     part highly dispersed silicic acid                      
            97    parts talc                                              
______________________________________
These dusts are formed by mixing the components then grinding the mixture to the desired particle size.
______________________________________                                    
5% granules:                                                              
           5      parts active compound                                   
           0.25   part epichlorohydrin                                    
           0.25   part cetyl polyglycol ether                             
           3.5    parts polyethylene glycol                               
           91     part kaolin (particle size 0.3-0.8 mm)                  
______________________________________
Granules are formed by mixing the active compound with epichlorohydrin and dissolving the mixture in 6 parts of acetone. The polyethylene glycol and cetyl polyglycol ether are then added. The resultant solution is sprayed on the kaolin and the acetone evaporated in vacuo.
Wettable powders:
______________________________________                                    
70%:     70     parts active compound                                     
         5      parts sodium dibutylnaphthylsulfonate                     
         3      parts naphthalenesulfonic                                 
                acid/phenolsulfonic                                       
                acid/formaldehyde condensate (3:2:1)                      
         10     parts kaolin                                              
         12     parts Champagne chalk                                     
40%:     40     parts active compound                                     
         5      parts sodium lignin sulfonate                             
         1      part sodium dibutylnaphthalene sulfonic                   
                acid                                                      
         54     parts silicic acid                                        
25%:     25     parts active compound                                     
         4.5    parts calcium lignin sulfate                              
         1.9    parts Champagne chalk/hydroxyethyl                        
                cellulose (1:1)                                           
         1.5    parts sodium dibutylnaphthalene                           
                sulfonate                                                 
         19.5   silicic acid                                              
         19.5   parts Champagne chalk                                     
         28.1   parts kaolin                                              
25%:     25     parts active compound                                     
         2.5    parts isooctylphenoxy-polyethylene-                       
                ethanol                                                   
         1.7    parts Champagne chalk/hydroxyethyl                        
                cellulose (1:1)                                           
         8.3    parts sodium aluminum silicate                            
         16.5   parts kieselguhr                                          
         46     parts kaolin                                              
10%:     10     parts active compound                                     
         3      parts of a mixture of sodium salts of                     
                saturated fatty alcohol sulfates                          
         5      parts naphthalenesulfonic acid/                           
                formaldehyde condensate                                   
         82     parts kaolin                                              
______________________________________
These wettable powders are prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
Emulsifiable concentrate:
______________________________________                                    
25%:      25     parts active substance                                   
          2.5    parts epoxidized vegetable oil                           
          10     parts of an alkylarylsulfonate/fatty                     
                 alcohol polyglycol ether mixture                         
          5      parts dimethylformamide                                  
          57.5   parts xylene                                             
______________________________________
The amount of the present compositions which constitute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredients varies from about 0.01 to about pounds per acre, preferably about 0.10 to about 10 pounds per acre with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.
EXAMPLES
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of this invention in any manner whatsoever.
EXAMPLE 1 Preparation of 4-chloro-3-(1-hydroxy-2',6'-dichlorobenzyl)-pyridine (Compound No. 11)
Eighteen grams of 4-chloro pyridine hydrochloride were placed into 100 ml of diethyl ether in a 500 ml beaker equipped with a magnetic stirrer. 6.5 grams of sodium hydroxide in 100 ml (milliliters) of water were added at 0° C. and the mixture stirred for 15 minutes. The diethyl ether layer was separated and washed with water, dried over magnesium sulfate and filtered and stripped. 5.7 grams of the 4-chloropyridine produced was placed into a 3-neck flask in 50 ml of ethylene glycol dimethyl ether and cooled to -70° C. Forty ml of lithium diisopropyl amide ("LDA") was added over a period of 30 minutes while the temperature maintained at -60° C. to produce an orange suspension. The reaction mixture was then stirred at -70° C. for one hour. 9.2 grams of 2,6-dichlorobenzaldehyde were added and the temperature maintained between -45° to -60° C. The reaction mixture was stirred in a dry ice bath for 2 hours, then left at room temperature overnight.
Thirty-five ml of saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture stirred for 15 minutes at room temperature. The solid was removed by filtration and washed twice, first with water, then with methylene chloride to yield 13.2 grams of 4-chloro-3-(1-hydroxy-2',6'-dichloro-2 benzyl)pyridine.
EXAMPLE 2 Preparation of 4-chloro-3-(1-N,N-dimethylcarbamyloxy-2',6'-dichloro-benzyl)-pyridine (Compound No. 77)
One gram of 4-chloro-3-(1-hydroxy-2',6'-dichlorobenzyl)-pyridine was dissolved in 20 ml of tetrahydrofuran in a 200 ml round bottom flask equipped with a magnetic stirrer. The solution was cooled in an ice bath, and 0.3 gram of sodium hydride added. The temperature was maintained at 0° C. and 0.55 ml of N,N-dimethyl carbamyl chloride added. The mixture was stirred at room temperature overnight, poured into ice and extracted with methylene chloride twice. The combined methylene chloride layers were separated and washed with water, dried with magnesium sulfate, filtered and stripped to yield a yellow oil, 4-chloro-3-(1-N,N-dimethylcarbamyloxy-2',6'-dichloro-benzyl)-pyridine.
EXAMPLE 3 Preparation of 2-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-4-trifluoromethyl-pyridin (Compound No. 13)
To a 3-neck flask equipped with a dropping funnel, a thermometer, and a condenser with a drying tube were added 5 grams of 2-chloro-4-trifluoromethyl pyridine and 5 ml of ethylene glycol dimethyl ether. The mixture was cooled to -70° C. and 22 ml of LDA were slowly added with the temperature maintained below -55° C. The reaction mixture was stirred at -70° C. for 1.5 hours, and 3.5 ml of 2-trifluoromethyl benzaldehyde added. The reaction mixture was stirred in a dry-ice bath, then at room temperature over night. Fifteen ml of saturated aqueous ammonium chloride solution was added, the solvent stripped and the oil residue washed with water and extracted with methylene chloride (3 times). The combined methylene chloride layers were washed with brine, dried and stripped to yield a brown oil. The brown oil was put onto a silica gel column and eluted with a 1:1 mixture of hexane and diethyl ether to yield 6.2 grams of 2-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-4-trifluoro methyl-pyridine.
EXAMPLE 4 Preparation of 2-chloro-3-[1-(4-morpholine)-carbonyloxy-2'-trifluoromethyl-benzyl]-4-trifluoromethyl pyridine (Compound No. 87)
To a 200 ml round bottom flask with magnetic stirrer reactor was added 1.0 gram of 2-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-4-trifluoromethyl pyridine dissolved in 20 ml tetrahydrofuran. The solution was cooled in ice, and 0.3 gram of sodium hydride added. 0.5 ml of morpholine carbamyl chloride was added at 0° C., and the mixture stirred at room temperature overnight. An orange participate formed and the mixture was poured into ice water, and extracted two times with methylene chloride. The combined methylene chloride layers were washed with water, dried (over magnesium sulfate), filtered and stripped to yield 1.5 grams of an orange solid, 2-chloro-3-[1-(4-morpholine)-carbonyloxy-2'-trifluoromethylbenzyl]-4-trifluoromethyl pyridine.
EXAMPLE 5 Preparation of 4-chloro-3-(1-N,N-diallylcarbamyloxy-2'-trifluoromethyl-benzyl)-pyridine (Compound No. 48)
To 4 grams of phosgene (20% in toluene) cooled in an ice bath were added, over a 5 minute period, 2 grams of 2-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-pyridine (produced in accordance with the process of Example 1 employing 2-trifluoromethyl benzaldehyde as a starting material) dissolved in 25 ml of tetrahydrofuran. One gram of triethylamine was added and the mixture stirred over night at room temperature. Seven ml of diallylamine were added to form a yellow suspension. This suspension was stripped and the mixture triturated in diethyl ether. The solid was filtered and rinsed with diethyl ether. The filtrate was stripped, put on a silica gel column, and eluted with a 10:1 hexane:ethyl acetate mixture to yield 2.25 grams of 4-chloro-3-(1-N,N-diallylcarbamyloxy-2'-trifluoromethyl-benzyl)-pyridine.
EXAMPLE 6 Preparation of 4-chloro-3-[1-(2-N-chloroethylcarbamyloxy)-2'-trifluoromethyl-benzyl]-pyridine (Compound No. 41)
To 1.2 grams of 4-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-pyridine dissolved in 10 ml of tetrahydrofuran were added 2 equivalents of 2-chloroethyl isocyanate along with 3 drops of triethylamine and 2 drops of dibutyl tin dilaurate. The mixture was stirred at room temperature overnight and, in 20 ml of methylene chloride were added with an additional 2 equivalents of 2-chloroethyl isocyanate, 3 drops of triethylamine and 2 drops of dibutyl tin dilaurate. The mixture was again stirred overnight; then poured into ice water; extracted twice with methylene chloride, dried and stripped. The residue was put onto a silica gel column and eluted with a 4:1 hexane:diethyl ether mixture to yield 0.9 grams of 4-chloro-3-[1-(2-N-chloroethylcarbamyloxy)-2'-trifluoromethylbenzyl]-pyridine.
EXAMPLE 7 Preparation of 4-chloro-3-(1-N,N-dimethylcarbamyloxy-2'-trifluoromethyl-benzyl)-pyridine (Compound No. 27)
1.5 grams of 4-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-pyridine were dissolved in 25 ml of tetrahydrofuran and cooled to 0° C. 0.5 gram of sodium hydride was added and the mixture stirred for 15 minutes. 0.75 ml of N,N-dimethyl carbamyl chloride was added and the mixture was stirred overnight at room temperature. The mixture was then poured into ice water and extracted with methylene chloride. The methylene chloride layer was washed with water, dried over magnesium sulfate, filtered and stripped to yield an orange colored solid. The solid was rinsed with hexane to yield 1.53 grams of 4-chloro-3-(1-N,N-dimethylcarbamyloxy-2'-trifluoromethyl-benzyl)-pyridine.
EXAMPLE 8 Preparation of 4-chloro-3-(1-trimethylacetoxy-2'-trifluoromethyl-benzyl)-pyridine (Compound No. 39)
2.0 grams of 4-chloro-3-(1-hydroxy-2'-trifluoromethyl-benzyl)-pyridine was dissolved in 40 ml of tetrahydrofuran and cooled to 0° C. 0.7 g of sodium hydride was added and the mixture stirred for 15 minutes. 1.30 ml of trimethyl acetyl chloride was added and the reaction was stirred overnight at room temperature. The reaction mixture was poured into ice water and extracted two times with methylene chloride. The combined methylene chloride layers were washed with water; dried over magnesium sulfate; filtered and stripped to yield a yellow oil, 4-chloro-3-(1-trimethylacetoxy-2'-trifluoromethyl-benzyl-pyridine.
EXAMPLE 9
Preparation of 4-chloro-3-(1-benzyloxy-2'-trifluoromethyl-benzyl)-pyridine
(Compound No. 57)
0.9 grams of sodium hydride (80% in white oil) was rinsed 4 times with 2 ml of tetrahydrofuran. Over a 2 minute period, 2.9 grams of 2-chloro-3-(1-hydroxy-2'-trifluoromethylbenzyl)-pyridine were added and the mixture refluxed for 5 minutes and stirred for 1 hour at ambient temperature. Benzyl bromide (1.7 ml) was added and the mixture stirred for 1 hour and then refluxed for 0.5 hour. 0.1 gram of sodium iodide was added and the mixture stirred for 0.5 hour. The mixture was then stripped and dissolved in a water/methylene chloride mixture. The organic layer was washed with brine and dried over magnesium sulfate. The product was filtered, stripped, placed on a silica gel column and eluted with a 1:2 hexane:ethylacetate blend to yield 3.2 grams of 4-chloro-3-(1-benzyloxy-2'-trifluoromethyl-benzyl)-pyridine.
EXAMPLE 10
Employing a process similar to those described above, the following compounds, listed in Table I, were prepared:
                                  TABLE I                                 
__________________________________________________________________________
 ##STR17##                                                   (I)          
COMP. NO.                                                                 
       n R.sup.1                                                          
               R.sup.2                                                    
                 R.sup.3                                                  
                   R.sup.4                                                
                     R.sup.5                                              
                           R.sup.6                                        
                                  R.sup.7                                 
                                       R.sup.8                            
                                         R.sup.9                          
                                             R                            
__________________________________________________________________________
Compounds where A is O                                                    
1      0 Cl    H H H CH.sub.3                                             
                           H      Cl   H H   H                            
2      0 Cl    H H H CH.sub.3                                             
                           H      H    H H   H                            
3      0 Cl    H H H OCH.sub.3                                            
                           H      OCH.sub.3                               
                                       H H   H                            
4      0 Cl    H H H CF.sub.3                                             
                           H      H    H H   H                            
5      0 Cl    H H H NO.sub.2                                             
                           H      CF.sub.3                                
                                       H H   H                            
6      0 Cl    H H H Cl    OCH.sub.2 CH.sub.3                             
                                  Br   H H   H                            
7      0 Br    H H H CF.sub.3                                             
                           H      H    H H   H                            
8      0 C.sub.4 H.sub.9                                                  
               H H H CF.sub.3                                             
                           H      H    H H   H                            
9      0 Cl    H H H Cl    H      H    H H   H                            
10     0 Cl    H H H Br    H      H    H H   H                            
11     0 Cl    H H H Cl    H      H    H Cl  H                            
12     1 Cl    H H H CF.sub.3                                             
                           H      H    H H   H                            
13     0 CF.sub.3                                                         
               H H Cl                                                     
                     CF.sub.3                                             
                           H      H    H H   H                            
14     0 Cl    H H H C.sub.2 H.sub.5                                      
                           H      H    H H   H                            
15     0 Cl    H H H CH.sub.3                                             
                           H      H    H CH.sub.3                         
                                             H                            
16     0 Cl    H H H OCH.sub.3                                            
                           H      H    H H   H                            
17     0 Cl    H H H OCF.sub.3                                            
                           H      H    H H   H                            
18     0 Cl    H H H F     H      H    H H   H                            
19     0 SCH.sub.3                                                        
               H H H CF.sub.3                                             
                           H      H    H H   H                            
20     0 Cl    H H H SC.sub.2 H.sub.5                                     
                           H      H    H H   H                            
21     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR18##                   
22     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR19##                   
23     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR20##                   
24     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR21##                   
25     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR22##                   
26     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR23##                   
27     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR24##                   
28     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR25##                   
29     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR26##                   
30     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR27##                   
31     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR28##                   
32     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR29##                   
33     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR30##                   
34     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR31##                   
35     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR32##                   
36     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR33##                   
37     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR34##                   
38     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR35##                   
39     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR36##                   
40     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR37##                   
41     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR38##                   
42     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR39##                   
43     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR40##                   
44     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR41##                   
45     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR42##                   
46     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR43##                   
47     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR44##                   
48     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR45##                   
49     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR46##                   
50     DIASTEREOMER OF COMPOUND 49                                        
51     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR47##                   
52     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR48##                   
53     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR49##                   
54     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR50##                   
55     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR51##                   
56     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR52##                   
57     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR53##                   
58     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR54##                   
59     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR55##                   
60     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR56##                   
61     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR57##                   
62     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR58##                   
63     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR59##                   
64     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR60##                   
65     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR61##                   
66     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR62##                   
67     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR63##                   
68     0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR64##                   
69     0 Cl    H H H Cl    OC.sub.2 H.sub.5                               
                                  Br   H H                                
                                              ##STR65##                   
70     0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR66##                   
71     0 Br    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR67##                   
72     0 Cl    H H H NO.sub.2                                             
                           H      CF.sub.3                                
                                       H H                                
                                              ##STR68##                   
73     0 Cl    H H H Cl    H      H    H H                                
                                              ##STR69##                   
74     0 Cl    H H H CH.sub.3                                             
                           H      Cl   H H                                
                                              ##STR70##                   
75     1 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR71##                   
76     0 Cl    H H H Br    H      H    H H                                
                                              ##STR72##                   
77     0 Cl    H H H Cl    H      H    H Cl                               
                                              ##STR73##                   
78     0 Cl    H H H C.sub.2 H.sub.5                                      
                           H      H    H H                                
                                              ##STR74##                   
70     0 Cl    H H H NO.sub.2                                             
                           H      H    H H                                
                                              ##STR75##                   
80     0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR76##                   
81     0 Cl    H H H OCF.sub.3                                            
                           H      H    H H                                
                                              ##STR77##                   
82     0 Cl    H H H F     H      H    H H                                
                                              ##STR78##                   
83     0 Cl    H H H SC.sub.2 H.sub.5                                     
                           H      H    H H                                
                                              ##STR79##                   
84     0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR80##                   
85     0 Cl    H H H Br    H      H    H H                                
                                              ##STR81##                   
86     0 Cl    H H H Cl    H      H    H Cl                               
                                              ##STR82##                   
87     0 CF.sub.3                                                         
               H H Cl                                                     
                     CF.sub.3                                             
                           H      H    H H                                
                                              ##STR83##                   
88     0 Cl    H H H C.sub.2 H.sub.5                                      
                           H      H    H H                                
                                              ##STR84##                   
89     0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR85##                   
90     0 Cl    H H H SC.sub.2 H.sub.5                                     
                           H      H    H H                                
                                              ##STR86##                   
91     0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR87##                   
92     0 Cl    H H H Br    H      H    H H                                
                                              ##STR88##                   
93     0 Cl    H H H Cl    H      H    H Cl                               
                                              ##STR89##                   
94     0 CF.sub.3                                                         
               H H Cl                                                     
                     CF.sub.3                                             
                           H      H    H H                                
                                              ##STR90##                   
95     0 Cl    H H H C.sub.2 H.sub.5                                      
                           H      H    H H                                
                                              ##STR91##                   
96     0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR92##                   
97     0 Cl    H H H CH.sub.3                                             
                           H      H    H CH.sub.3                         
                                              ##STR93##                   
98     0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR94##                   
99     0 Cl    H H H C.sub.2 H.sub.5                                      
                           H      H    H H                                
                                              ##STR95##                   
100    0 Cl    H H H SC.sub.2 H.sub.5                                     
                           H      H    H H                                
                                              ##STR96##                   
101    0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR97##                   
102    0 Cl    H H H NO.sub.2                                             
                           H      H    H H                                
                                              ##STR98##                   
103    0 Cl    H H H OCF.sub.3                                            
                           H      H    H H                                
                                              ##STR99##                   
104    0 Cl    H H H OCH.sub.3                                            
                           H      H    H H                                
                                              ##STR100##                  
105    0 Cl    H H H NO.sub.2                                             
                           H      H    H H                                
                                              ##STR101##                  
106    0 Cl    H H H OCF.sub.3                                            
                           H      H    H H                                
                                              ##STR102##                  
107    0 Cl    H H H F     H      H    H H                                
                                              ##STR103##                  
108    0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR104##                  
109    0 Cl    H H H Br    H      H    H H                                
                                              ##STR105##                  
110    0 Cl    H H H Cl    OC.sub.2 H.sub.5                               
                                  Br   H H                                
                                              ##STR106##                  
111    0 Cl    H H H NO.sub.2                                             
                           H      CF.sub.3                                
                                       H H                                
                                              ##STR107##                  
112    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR108##                  
113    0 Cl    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.3                     
114    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR109##                  
115    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR110##                  
116    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR111##                  
117    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR112##                  
118    0 Cl    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.2 CH.sub.3            
119    0 Cl    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.2C(Cl)CH.sub.2        
120    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR113##                  
121    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR114##                  
122    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR115##                  
123    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR116##                  
124    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR117##                  
125    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR118##                  
126    0 Cl    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.2C(Cl)CH              
127    0 Cl    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.2C(Cl) (Br)CH.sub.2   
128    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR119##                  
129    0 SCH.sub.3                                                        
               H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR120##                  
130    0                                                                  
          ##STR121##                                                      
               H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR122##                  
131    0                                                                  
          ##STR123##                                                      
               H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR124##                  
132    0 Cl    H H H Cl    H      H    H H                                
                                              ##STR125##                  
133    0 Cl    H H H Cl    H      H    H H                                
                                              ##STR126##                  
134    0 Cl    H H H OCF.sub.3                                            
                           H      H    H H                                
                                              ##STR127##                  
135    0 Cl    H H H CH.sub.2 CH.sub.3                                    
                           H      H    H H                                
                                              ##STR128##                  
136    0 Cl    H H H Cl    H      H    H H                                
                                              ##STR129##                  
137    0 Cl    H H H Br    H      H    H H                                
                                              ##STR130##                  
138    0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR131##                  
139    0 Cl    H H H Br    H      H    H H                                
                                              ##STR132##                  
140    0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR133##                  
141    0 Cl    H H H CH.sub.3                                             
                           H      H    H H                                
                                              ##STR134##                  
Compounds where A is S                                                    
142    0 Cl    H H H CF.sub.3                                             
                           H      H    H H                                
                                              ##STR135##                  
143    0 OH    H H H CF.sub.3                                             
                           H      H    H H   CH.sub.3                     
__________________________________________________________________________
HERBICIDAL SCREENING TESTS
The compounds listed in the foregoing table were tested for herbicidal activity by various methods and at various rates of application. The results of some of these tests are given below. As one skilled in the art is aware, the results obtained in herbicidal screening tests are affected by a number of factors that are not readily controllable. Environmental conditions, such as amount of sunlight and water, soil type, soil pH, temperature and humidity, are examples of such factors. Other factors which can affect test results are the depth of planting and the application rate of the herbicide, as well as the nature of the crops being tested. Results will also vary from crop to crop and within the crop varieties.
PRE-EMERGENCE HERBICIDAL SCREENING TEST
On the day preceding treatment, seeds of several different weed species were planted in sandy loam soil at a depth of 0.5 inch (1.3 cm) in individual rows using one species per row across the width of a flat. The soil was fortified with 17-17-17 fertilizer (N--P2 O5 --K2 O) on a weight basis and pasteurized. The weeds planted were wild oat (Avena fatua) (AVEFA), barnyardgrass (Echinochloa crusgalli) (ECHCG), green foxtail (Setaria viridis) (SETVI), velvetleaf (Abutilon theophrasti) (ABUTH), morningglory species (Ipomoea spp.) (IPOSS) and wild mustard (Sinapsis arvensis) (SINAR). Plant densities ranged from 3 to 25 plants per row, depending upon the size of the plants.
Solutions of the test compounds were made by weighing out 74.7 or 18.8 milligrams (mg) of the test compound into a 60 ml wide-mouth bottle, then dissolving the compound in 7.0 ml acetone containing 1% Tween 20® (polyoxyethylene sorbitan monolaurate emulsifier) and then adding 7 ml of deionized water to reach a 14 ml final volume. Tween 20® content was 0.5% v/v of the final spray volume. Additional solvents, not exceeding 2 ml, were used if needed to dissolve the compound.
The soil surface was sprayed inside an enclosed linear spray table. The flats were sprayed with the spray solution calibrated to deliver 748 L/ha. The application rate was 4.0 or 1.0 kg/ha.
The flats were placed into a greenhouse at 21°-29° C. and water daily by sprinkling. The degree of weed control was visually assessed and recorded 17-21 days after treatment, as percentage control compared to the growth of the same species of the same age in an untreated check flat.
The results of such pre-emergent testing are summarized in Table II below.
POST-EMERGENCE HERBICIDAL EVALUATION
The soil was prepared and seeded with the same species and methodology described for the pre-emergence test. The flats were placed in the greenhouse at 21°-29° C. and watered by sprinkling. The seeds of the weed species were planted 10-12 days before treatment. In general, grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage. Watering of the treated flats was confined to the soil surface and not to the foliage of the germinated plants. The degree of weed control was visually assessed and recorded 17-21 days after treatment, as percentage control compared to the growth of the same species in an untreated check flat of the same age.
The percent control is the total injury to the plants due to all factors, including inhibited germination, killing of the plant tissue after emergence, stunting, malformation, chlorosis and other types of injury. The control ratings vary from 0 to 100 percent, where 0 represents no effect with growth equal to the untreated control, and 100 represents complete kill; a dash indicates that a test was not performed at that level of application.
The results are listed in Table III below.
                                  TABLE II                                
__________________________________________________________________________
Pre-Emergent - Testing (4.0 kg/ha)                                        
COMP. NO.                                                                 
        AVEFA                                                             
             ECHCG SETVI                                                  
                        ABUTH                                             
                             IPOSS                                        
                                  SINAR                                   
__________________________________________________________________________
1       0    0     --*  0    0    0                                       
2       0    0     --*  0    0    0                                       
3       0    0     0    0    0    0                                       
4       10   98    10   30   30   10                                      
5       0    0     0    0    0    0                                       
6       0    0     0    0    0    0                                       
7       0    98    15   70   20   25                                      
8       0    0     0    0    0    0                                       
9       0    0     0    0    0    0                                       
10      5    50    10   5    10   0                                       
11      0    0     0    0    10   0                                       
12      0    10    10   0    10   0                                       
13      0    10    10   0    10   0                                       
14      5    100   20   40   40   25                                      
15      40   95    15   60   20   30                                      
16      30   5     100  0    0    0                                       
17      10   98    10   60   60   15                                      
18      0    0     0    0    0    0                                       
19      15   90    90   0    0    0                                       
20      0    98    0    10   10   20                                      
21      20   100   10   40   10   20                                      
22      50   98    40   60   10   40                                      
23      5    0     70   10   0    0                                       
24      10   98    100  90   80   50                                      
25      0    25    95   70   10   60                                      
26      5    98    20   70   50   0                                       
27      20   100   100  98   95   75                                      
28      5    98    10   60   0    10                                      
29      5    98    80   70   5    15                                      
30      5    100   20   70   20   20                                      
31      95   100   100  98   95   90                                      
32      95   100   100  100  98   85                                      
33      5    100   100  85   90   20                                      
34      10   25    100  75   5    10                                      
35      60   100   80   85   95   25                                      
36      25   100   95   30   60   20                                      
37      98   100   100  98   95   80                                      
38      60   100   100  90   95   70                                      
39      98   100   100  95   95   90                                      
40      0    90    95   60   80   5                                       
41      98   100   100  98   95   60                                      
42      98   100   100  100  95   90                                      
43      50   100   30   --*  15   30                                      
44      5    100   20   60   20   10                                      
45      98   100   100  100  95   70                                      
46      98   100   100  100  95   85                                      
47      75   100   100  70   85   75                                      
48      15   100   100  60   90   50                                      
49      0    10    100  40   10   15                                      
50      0    0     10   5    5    10                                      
51      0    10    100  0    0    10                                      
52      98   100   100  98   95   80                                      
53      98   100   100  70   90   40                                      
54      20   100   30   50   20   60                                      
55      0    0     0    0    5    0                                       
56      0    0     0    5    5    10                                      
57      60   100   100  95   100  85                                      
58      40   100   100  70   100  40                                      
59      10   100   100  70   5    10                                      
60      95   100   100  100  95   75                                      
61      40   100   100  5    10   0                                       
62      95   100   100  70   95   40                                      
63      90   100   100  60   95   60                                      
64      0    0     0    0    0    0                                       
65      98   100   100  98   95   75                                      
66      10   100   100  60   90   30                                      
67      98   100   100  90   90   75                                      
68      60   100   60   80   30   70                                      
69      5    70    25   5    10   30                                      
70      85   100   100  90   95   60                                      
71      0    0     0    0    0    0                                       
72      0    10    10   5    0    0                                       
73      70   100   100  90   90   40                                      
74      5    95    90   10   10   0                                       
75      80   100   100  60   80   10                                      
76      25   100   100  100  95   30                                      
77      5    100   100  60   50   15                                      
78      95   100   100  90   100  85                                      
79      25   100   100  100  0    25                                      
80      25   100   100  50   90   5                                       
81      90   100   100  95   95   60                                      
82      40   100   100  70   85   5                                       
83      0    100   98   60   90   20                                      
84      70   100   100  90   98   60                                      
85      60   100   100  100  95   90                                      
86      20   100   100  100  95   25                                      
87      0    5     0    5    10   0                                       
88      98   100   100  100  95   60                                      
89      90   100   100  90   100  60                                      
90      30   100   98   70   90   10                                      
91      98   100   100  70   90   50                                      
92      98   100   100  100  98   75                                      
93      70   100   100  15   90   15                                      
94      0    10    0    0    0    0                                       
95      100  100   100  100  98   100                                     
96      98   100   100  75   95   50                                      
97      95   100   100  30   98   15                                      
98      85   100   100  80   95   50                                      
99      98   100   100  90   95   85                                      
100     40   100   98   50   40   20                                      
101     15   100   100  0    15   5                                       
102     0    100   100  0    0    0                                       
103     75   100   100  60   90   20                                      
104     85   100   100  60   95   20                                      
105     85   100   100  30   30   30                                      
106     100  100   100  100  95   70                                      
107     50   100   100  25   85   10                                      
108     5    15    20   5    5    10                                      
109     10   10    20   0    5    40                                      
110     0    0     40   0    0    0                                       
111     0    0     0    0    0    0                                       
112     95   100   100  90   95   85                                      
113     10   85    100  10   5    10                                      
114     75   100   100  90   90   50                                      
115     80   100   100  90   90   60                                      
116     5    100   100  85   90   60                                      
117     50   100   100  95   90   80                                      
118     20   100   100  10   15   5                                       
119     10   100   100  75   90   60                                      
120     10   100   95   10   0    20                                      
121     0    60    100  20   10   10                                      
122     0    70    98   10   0    20                                      
123     5    100   100  50   10   30                                      
124     30   100   100  70   50   60                                      
125     20   100   100  85   90   80                                      
126     5    10    60   0    0    10                                      
127     20   100   100  60   5    90                                      
128     15   100   100  75   80   60                                      
129     10   30    98   0    5    30                                      
130     25   70    98   30   30   10                                      
131     10   95    98   50   75   20                                      
132     90   100   100  70   95   60                                      
133     95   100   100  85   95   50                                      
134     90   100   100  90   90   90                                      
135     70   100   100  90   95   80                                      
136     25   100   100  50   90   50                                      
137     30   100   100  70   90   50                                      
138     30   100   100  90   90   90                                      
139     80   100   100  80   90   30                                      
140     90   100   100  50   80   75                                      
141     25   100   100  90   98   90                                      
142     0    10    60   0    40   10                                      
143     15   20    80   15   0    10                                      
__________________________________________________________________________
 * -- indicates not tested                                                

                                  TABLE III                               
__________________________________________________________________________
Post-Emergent - Testing (4.0 kg/ha)                                       
COMP. NO.                                                                 
        AVEFA                                                             
             ECHCG SETVI                                                  
                        ABUTH                                             
                             IPOSS                                        
                                  SINAR                                   
__________________________________________________________________________
1       0    0     0    0    0    0                                       
2       0    0     0    0    0    0                                       
3       0    0     0    0    0    0                                       
4       0    70    20   0    10   0                                       
5       0    0     0    0    0    0                                       
6       0    0     0    0    0    0                                       
7       0    95    20   5    30   5                                       
8       0    0     0    0    5    15                                      
9       0    0     0    0    5    0                                       
10      0    0     0    0    20   10                                      
11      5    10    10   0    0    0                                       
12      0    0     10   0    5    0                                       
13      0    0     10   0    5    0                                       
14      10   70    30   5    80   10                                      
15      0    0     0    5    15   0                                       
16      0    0     0    0    5    0                                       
17      5    5     15   10   15   10                                      
18      0    0     0    0    0    0                                       
19      0    0     0    0    10   0                                       
20      0    0     0    0    15   5                                       
21      0    25    5    15   10   0                                       
22      10   90    15   5    90   5                                       
23      5    0     70   10   0    0                                       
24      5    0     25   100  85   75                                      
25      0    0     0    85   85   20                                      
26      10   95    5    10   60   0                                       
27      85   98    85   100  95   85                                      
28      10   95    5    0    20   0                                       
29      10   98    10   5    30   0                                       
30      0    98    5    90   90   0                                       
31      90   98    90   95   90   80                                      
32      15   95    85   90   90   80                                      
33      5    80    85   95   90   60                                      
34      15   10    25   85   60   15                                      
35      10   98    60   98   90   40                                      
36      10   70    50   80   90   75                                      
37      95   98    90   98   90   85                                      
38      5    98    40   98   90   75                                      
39      90   98    85   100  90   85                                      
40      25   30    30   95   90   60                                      
41      90   98    90   98   90   90                                      
42      90   95    90   90   90   90                                      
43      20   95    20   30   30   5                                       
44      0    50    20   60   60   10                                      
45      90   100   90   95   90   85                                      
46      90   98    90   95   90   75                                      
47      5    98    60   10   20   70                                      
48      15   100   80   98   95   80                                      
49      5    10    15   60   60   30                                      
50      0    0     20   10   15   0                                       
51      0    0     20   60   80   15                                      
52      95   100   98   95   90   75                                      
53      60   100   90   95   90   60                                      
54      75   100   30   75   85   10                                      
55      0    10    0    20   20   70                                      
56      0    0     0    5    25   15                                      
57      20   98    95   95   95   95                                      
58      60   100   98   98   90   80                                      
59      5    98    20   10   15   5                                       
60      75   100   98   100  90   80                                      
61      15   40    30   30   85   15                                      
62      70   95    95   98   90   50                                      
63      85   98    95   50   85   60                                      
64      0    0     0    0    5    5                                       
65      95   100   95   98   95   60                                      
66      15   20    40   80   90   75                                      
67      60   98    85   85   90   50                                      
68      10   98    15   30   10   20                                      
69      0    0     0    75   90   75                                      
70      70   98    90   95   90   70                                      
71      0    0     0    0    0    0                                       
72      0    5     15   30   10   10                                      
73      5    95    90   95   90   40                                      
74      5    25    10   75   20   20                                      
75      10   40    60   98   90   70                                      
76      90   98    90   95   90   90                                      
77      10   50    70   80   75   80                                      
78      90   100   95   95   85   75                                      
79      15   100   85   80   85   30                                      
80      30   95    85   85   90   25                                      
81      95   98    90   100  90   40                                      
82      5    95    90   60   90   75                                      
83      5    70    85   95   90   60                                      
84      85   95    75   80   90   60                                      
85      50   95    75   50   80   30                                      
86      30   100   70   60   85   30                                      
87      0    0     0    0    5    0                                       
88      90   98    90   95   90   80                                      
89      90   98    90   90   85   50                                      
90      15   95    60   95   90   25                                      
91      90   95    80   90   90   60                                      
92      95   100   90   95   90   75                                      
93      40   40    15   30   60   50                                      
94      0    0     0    0    0    0                                       
95      90   98    90   98   90   70                                      
96      95   98    98   98   85   40                                      
97      90   98    95   60   85   15                                      
98      100  100   100  98   85   60                                      
99      98   100   100  98   90   95                                      
100     25   95    75   90   90   20                                      
101     60   75    30   75   85   75                                      
102     10   100   85   70   90   20                                      
103     50   100   95   90   95   60                                      
104     98   100   98   90   80   50                                      
105     60   100   85   50   20   10                                      
106     90   98    95   100  90   60                                      
107     40   85    90   30   95   20                                      
108     20   20    30   60   60   40                                      
109     5    25    15   60   75   80                                      
110     0    0     0    25   25   15                                      
111     0    0     0    10   10   0                                       
112     90   95    90   98   90   80                                      
113     0    0     10   15   20   0                                       
114     80   98    90   98   90   70                                      
115     85   98    90   90   90   60                                      
116     70   98    85   70   90   30                                      
117     5    95    90   98   95   85                                      
118     10   10    20   20   80   15                                      
119     5    98    85   90   90   80                                      
120     0    10    50   50   90   85                                      
121     0    0     30   70   85   15                                      
122     0    5     20   80   90   60                                      
123     0    5     10   95   75   75                                      
124     20   98    30   90   70   80                                      
125     10   50    80   95   90   25                                      
126     5    20    60   90   90   85                                      
127     15   25    60   70   95   80                                      
128     25   90    60   75   95   80                                      
129     0    10    20   60   85   30                                      
130     10   40    85   98   90   10                                      
131     5    60    85   90   90   10                                      
132     95   100   95   85   90   90                                      
133     90   98    90   85   85   80                                      
134     90   98    90   98   90   90                                      
135     50   95    90   95   90   90                                      
136     20   98    85   75   90   50                                      
137     15   95    90   90   90   70                                      
138     20   98    90   90   95   70                                      
139     90   98    90   95   90   70                                      
140     75   98    90   75   85   60                                      
141     10   60    60   60   60   80                                      
142     0    0     10   60   90   50                                      
143     0    5     10   30   60   5                                       
__________________________________________________________________________
The results above illustrate the preemergent and postemergent efficacy of the present compounds against a variety of grasses and broadleaf species.

Claims (13)

What is claimed is:
1. An herbicidal composition comprising:
(A) a compound of the formula: ##STR136## wherein: R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen, C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 --C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C2 -C6 alkenyl, C2 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)alkoxycarbonyl(C1 -C6)alkyl; hydroxycarbonyl(C1 -C6)alkyl; or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio or C1 -C6 alkoxy; and
m is 0, 1 or 2;
or an agriculturally acceptable salts thereof;
(B) a co-herbicide selected from the group consisting of anilide herbicides, triketone and cyclohexanedione herbicides, imidazolidinone herbicides, sulfonylurea herbicides and phenoxyphenoxypropionate herbicides; and
(C) a carrier therefor.
2. A composition in accordance with claim 1 wherein R1 is halogen.
3. A composition in accordance with claim 2 wherein R1 is chloro or bromo.
4. A composition in accordance with claim 2 wherein R2, R3 and R4 are hydrogen.
5. A composition in accordance with claim 1 wherein R5 is halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 haloalkoxy, C1 -C6 alkoxy, nitro, or --S(O)m alkyl wherein m is 0, 1 or 2.
6. A composition in accordance with claim 5 wherein R6, R7, R8 and R9 are each independently hydrogen, C1 -C6 alkyl, halogen or C1 -C6 alkoxy.
7. A composition in accordance with claim 1 wherein R is phenyl-(C1 -C3)alkyl or is of the formula ##STR137## wherein R12 is C1 -C12 alkyl, C1 -C6 haloalkyl, phenyl or is of the formula ##STR138## wherein R13 and R14 are each independently C1 -C12 alkyl, hydrogen, C2 -C12 alkenyl, C2 -C12 alkynyl, phenyl, C1 -C12 haloalkyl, C1 -C6 alkoxy, (C1 -C6)alkoxy(C1 -C6)alkyl or R13 and R14 together with the ring to which they are bound form a morpholine, piperidine or pyrrolidine ring.
8. A composition in accordance with claim 7 wherein R is benzyl or is of the formula ##STR139## wherein R12 is C1 -C6 alkyl or is of the formula ##STR140## wherein R13 and R14 are each independently hydrogen, phenyl, C1 -C6 haloalkyl or C1 -C6 alkyl or together R13 and R14 form a morpholine ring.
9. A composition in accordance with claim 1 wherein:
R1 is halogen;
R2, R3 and R4 are hydrogen;
R5 is halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 haloalkoxy, C1 -C6 alkoxy, nitro or --S(O)m (C1 -C3)alkyl wherein m is 0, 1 or 2;
R6, R7, R8 and R9 are each independently hydrogen, C1 -C6 alkyl, halogen or C1 -C6 alkoxy; and
R is phenyl-(C1 -C3)alkyl or is of the formula ##STR141## wherein R12 is C1 -C12 alkyl, C1 -C6 haloalkyl, phenyl or is of the formula ##STR142## wherein R13 and R14 are each independently C1 -C12 alkyl, hydrogen, C2 -C12 alkenyl, phenyl, C2 -C12 alkynyl, C1 -C12 haloalkyl, C1 -C6 alkoxy, (C1 -C6)alkoxy(C1 -C6)alkyl or R13 and R14 together with the nitrogen to which they are bound form a morpholine, piperidine or pyrrolidine ring.
10. A composition in accordance with claim 1 wherein:
R1 is chloro or bromo;
R5 is trifluoromethyl, trifluoromethoxy, chloro, bromo, methoxy, methyl or ethyl;
R2, R3, R4, R7 and R8 are hydrogen;
R6 and R9 are each independently hydrogen, chloro or methyl; and
R is benzyl or is of the formula ##STR143## wherein R12 is C1 -C6 alkyl or is of the formula ##STR144## wherein R13 and R14 are independently hydrogen, phenyl, C1 -C6 haloalkyl or C1 -C6 alkyl or together R13 and R14 form a morpholine ring.
11. A composition according to claim 1, wherein said co-herbicide is selected from the group consisting of metolachlor, imazaquin, bensulfuron and the methyl ester thereof, chlorosulfuron and dichlofop.
12. A method for controlling undesirable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a an herbicidal composition comprising:
(A) a compound of the formula: ##STR145## wherein: R1 and R5 are each independently halogen, C1 -C6 haloalkyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, --OH, thiocyano, nitro or --N(R11)(R12);
R2, R3 and R4 are each independently hydrogen, C1 -C6 alkyl, nitro, halogen, C1 -C6 alkoxy, C1 -C6 haloalkoxy, C1 -C6 haloalkyl or --S(O)m --R10 ;
R6, R7, and R8 are each independently hydrogen, halogen, C1 -C6 alkyl, C2 -C6 alkenyl, C2 -C6 alkynyl, nitro, --N(R11)(R12), C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, halo(C1 -C6)alkoxy-(C1 -C6)alkyl, cyano, --C(X)--R10 or --S(O)m --R10 ;
R9 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy, (C1 -C6)alkoxy-(C1 -C6)alkyl, --S(O)m --R10, cyano, hydroxy, thiocyano, nitro or --N(R11)(R12);
A is oxygen or sulfur;
n is 0 or 1;
R is hydrogen, hydrocarbyl, hydrocarbyl substituted with one or more of halogen or C1 -C6 alkoxy or is of the formula --C(X)--R10, --C(O)--C(O)--R10, --S(O)2 --R10 or --P(X)(R15)(R16);
wherein:
X is O or S;
R10 is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, hydrocarbyl-S--, substituted hydrocarbyl-S-- or is of the formula --N(R11)(R12);
wherein R11 and R12 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, pyridyl, furyl, thienyl, (C1 -C6)alkoxycarbonyl(C1 -C6)alkyl, hydroxycarbonyl(C1 -C6)alkyl, or N(R13)(R14) wherein R13 and R14 are each independently hydrogen, C1 -C6 alkyl or phenyl;
or R11 and R12 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine or pyrrolidine ring, any of which may be optionally substituted with C1 -C6 alkyl;
R15 and R16 are each independently C1 -C6 alkyl, C1 -C6 alkylthio or C1 -C6 alkoxy; and
m is 0, 1 or 2;
or an agriculturally acceptable salt thereof;
(B) a co-herbicide selected from the group consisting of anilide herbicides, triketone and cyclohexanedione herbicides, imidazolidinone herbicides, sulfonylurea herbicides and phenoxyphenoxypropionate herbicides; and
(C) a carrier therefor.
13. A method according to claim 12, wherein said co-herbicide is selected from the group consisting of metolachlor, imazaquin, bensulfuron and the methyl ester thereof, chlorosulfuron and dichlofop.
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